Process for breaking petroleum emulsions



Patented May 25, 1948 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, and Arthur F r Wirtel, Glendale, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application July 13, 1945, Serial No. 605,002

9 Claims. (01. 252-341) 2 This invention relates to the resolution of petroleum emulsions.

One object of our-invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brinesrdispersed in'a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

Another object of our invention is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification, under the conditions just mentioned, are of significant value in removing impurities, particularly inorganic salts from pipeline oil. 7

And still another object of our invention isto provide a new demulsifier for petroleum emulsions of the water-in-oil type.

Demulsification, as contemplated in the present application, includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion, in absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.

The new demulsifier herein described, consists of an ester derived by reaction between diglycollic acid and a basic acylated aminoalcohol, in which there is at least one occurrence of the radical in which RC is the acyl radical of a monocarboxy detergent-forming acid having at least 8 and not more than 32 carbon atoms; the amino nitrogen atom is basic; R is an alkylene radical having at least 2 and not more than 10 carbon atoms; and n is a small whole number varying from 1 to 10; and the molecular weight of said compound in monomeric form, being at least 243 and not over 4,000; said amino compound being selected from the class consisting of anhydro base, the hydrated base, and salts.

Thus, one oi the reactants employed .in the manufacture of the ester herein described, consists of acylated aminoalcohols in which an acyloxy radical derived from a detergent-forming acid having from 8 to 32 carbon atoms is joined to a basic nitrogen atom by a carbon atom chain, or a carbon atom chain which is interrupted at least once by an oxygen atom. The aminoalcohols may have more than one amino radical, or, for that matter, more than one basic amino radical. The compounds herein contemplated as break-inducers are well known compounds and areproduced by conventional procedures. Stated another way, the compounds herein contemplated are esters'o'f aminoalcohols which may contain ether linkages, as well as more thanone amino nitrogen atom.

Reference to a basic amino nitrogenatom is used in its conventional sense. (Unsaturated groups, or negative groups, if substituted for one or more of the hydrogens of ammonia, reduce the basicity of the nitrogen atom to a remarkable degree. In general, the presence of one negative group linked to the nitrogen is suificient to destroy the ordinary basic properties. Textbook of Organic Chemistry, Richter, 2nd edition, page 253.)

Reference to an amine and the subsequent amino compounds is intended to include the salts and the anhydro base, as well as the hydrated base, since both obviously are present when an aqueous system is being subjected to the reagent, or when thereagent is used as a water solution or dispersion; (In an aqueous solution of the amine, the anhydro base, R-N'Hz, the hydrated base, RNH3OH, and the two ions are'all present. Richter, s'. v., page 252.) E

As has been previously stated, the reagents or break-inducers herein contemplated for employment in the present process are old and'wellknown products. For convenience and for purpose of brevity, reference is made to the'foll'ow ing th'ree United States patents to De Groote and Keiser, to wit, Nos. 2,324,488, 2,324,489 and 2,324,- 490, all dated July 20, 1943. Said patents are concerned with processes for breaking water-inoil emulsions. The demulsifying agent employed is in each instance the resultant derived by reaction between a certain fractional ester and an acylated aminoalcohol. The aminoalcohols described collectively in the aforementionedfthree ent. Subsequent reference will be made to this particular type, and examples will be included.

Aforementioned U. S. Patent' No. 2,324,488 describes hydroxylated acylated amino-ether compounds, containing:

(a) A radical derived from: a* basic hydr-oxy-- aminoether, and said radicalbein of the'kind containing at least one amino nitrogen free from attached aryl and amido-linked. acyl radicals;

said hydroxyaminoether radical being further characterized by the presence of at least one radical derived from a basic hydroxyarnine and.

being attached by at least one ether linkage to at least one radical selected from'the. class consisting of glycerol: radicals, polyglycerol radicals, glycol radicals; polyglycol .radicals,:basic hydroxyamine radicals, amido hydroxyamine radicals, and arylalkanolamine radicals; said basic hy-' droxyaminoet-herradical being characterizedby containing notmore than; 60- carbon atoms; and

(b) An acyl radical derived-from;-a detergentformingmonocarboxy acid having: at least 8- carbon atoms and: not more than 32 carbon atoms, said acylated aminoether being additionally characterized by the fact that said aforementionedacyl radical is a-substit-uent for a hydrogen atom' of an alcoholic hydroxyl radical.

AforementionedU. S; Patent No. 2,324,489 describes hydroxylated acylated monoamino compounds free from ether linkages, said hydroxylatedacylated amino compounds being-of thefollowingtype:

in which RCOO represents the oxyacyl radical derived from a monobasic detergent-forming acid; T represents a member of the class consisting of hydrogen atoms; nonhydr-oxy hydrocarbon radicals, andacylated radicals,- obtained by replacing ahydroge atom of the hydroxyl group-of an alkylolradicalby'the acyl radical of a monobasic carboxy acid: having, less than 8 car-- bon atoms; rt-represents a small whole number which is less than 10; mrepresentsthe numeral 1,2 M3; 712 represents'the numeral-0," 1 or 2; and m" represents thenumeral-O, 1- or 2'; with the proviso-thatm+m'+'m"=3;

Aforementioned U; S. Patent No; 2,324,490 de'- scribes basic hydroxylatedacylated" polyamine compounds free from ether linkages, said compounds having the following formula:

in which n represents a small whole number varying from 2' to 10; a: is a small whole number varyihgafrom il-to 10; Z is amember of the" class consisting of H; RC0;v RCO; and D; in which '4 RC0 represents an acyl radical derived from a detergent-forming monocarboxy acid; R'CO is an acyl radical derived from a lower molecular weight carboxy acid having 6 carbon atoms or less; and D is a member of the class consisting of alkyl, hydroxyalkyl, aminoalkyl, and acyloxyalkylene, in which instance the acyl group is a member of the class consisting of RC0 and 28/00; and the 'acylated polyamine is further characterized by the fact that there. must be present a member of the class consisting of (a) Acyloxyalkylene radicals, in which the acyl group is RC0; and (1)) Joint occurrence of an amino radical, in which thev acyl group is RC0 and a hydroxyalkyl radical. .A description. of certain high molal monocarboxy acids; andmore particularly, those commonly referred'toas detergent-forming monocarboxy acids,- app'ea'rs in all three of the aforementioned U. Spatents. .For convenience, the following description is substantially a verbatim form of the same subject-matter as it appears in U. S.

PatentNoi 2,324,490.

It is well known that certain monocarboxy organic acids containing 8-carbon atoms or more, and not 'more than 32 carbon atoms arecharacterizedbythe fact that they combine with alkalis to produce soap or soap like materials. These detergent-forming. acids include fatty acids, resin acids; petroleum acids etc. For the sake of convenience, these acids will be indicated by the formula R.COOI-I. Certain-derivatives of detergent-forming acids react withalkali torproduce' soapor soap-like materials, and are the obvious equivalent of the unchanged orunmodified detergent-forming acids. For instance, instead of fattyacids, one might-employ the chlorinatedfatty acids. Insteadof the resin acids, one might employ; the hydrogenatedresirr acids. Instead of naphthenic acids, one might'employ brominatednaphthenic acids,-.etc.

The fatty acids are ofthe type commonly re'- ferred to as higher fatty acids, andaoficourseathis is also true in-regard to derivatives of the kind indicated, insofar that such derivatives are obtained from higher fatty acids. The petroleum acids include not only naturally-occurring naphthenic acids, but also acids obtainedbythe-oxidation of- Wax, paraflimetc. Such-acids may'have as many as 32 carbon atoms. For instance, see U. S. Patent No. 2,242,837, dated May 20, 1941-, to

Shields.

We-have' found that the-composition of matter herein described and employed as the intermedia-te of our process, is preferably derived from unsaturated fatty acids having 18 carbon atoms. Such unsaturated fatty acids include oleic acid, ricinoleic acid; linoleic acid; linolenic acid,.i etc. One may employ mixed fatty acids, as-for example, the fatty acids obtained from hydrolysis-of cottonseed oil, soyabean. oil, etc. Our preferred intermediate or raw material is obtained from unsaturated fatty acids, and more especially, un saturated fatty acids containing. a hydroxylradical, or unsaturated fatty acids which have been subjected to oxidation. In addition to synthetic carboxy acids obtained by theoxidation of: paraffins or the like, there is a somewhat analogous class obtained by treating carbon dioxide or carbon monoxide, in the presence of hydrogen oran olefine, with steam, or by causing 9, halogenated hydrocarbon to react with potassium cyanide and saponifying the product obtained. Such products or mixtures. thereof, having atzleast 8wandinot more than 32 carbon atoms, and having at least one carboxyl group or the equivalent thereof, are suitable as detergent-forming monocarboxy acids; and another analogous class equally suitable is the mixture of carboxylic acids obtained by the alkali treatment of alcohols 01 high molecular weight formed in the catalytic hydrogenation of carbon monoxide.

As is well known, one need not use a high molal monocarboxy acid, such as a fatty acid, for introduction of the acyl group or acyloxy group. Any suitable functional equavalent, such as the acyl halide, the anhydride, ester, amide, etc., ma be employed.

The intermediate or raw material employed in the present process consists of an aminoalcohol ester, as described; and particular attention is called to the fact previously noted, that such esterified aminoalcohol must contain a hydroxyl radical to permit reaction with diglycollic acid. Other aminoalcohol esters of the kind herein contemplated as reactants are described in U.'S. Patent No. 2,259,704, dated October 21, 1941, to Monson and Anderson.

In light of what has been said, it hardly appears necessary to include a list of reactants and reagents derivable therefrom. Thus, suitable ter-' tiary amines, which may be employed, include the following: Triethanolamine, diethanolalky1-' amines, such as diethanolethylamine, diethanolpropylamine, etc. Other examples include diethanolmethylamine, tripropanolamine, dipropanolmethylamine, ,cyclohexanoldiethanolamine, dicyclohexanolethanolamine, cyclohexyldiethanolamine, dicyclohexylethanolamine, dicyclohexanolethylamine, benzyldiethanolamine, benzyldipropanolamine, tripentanolamine, trihexanolamine, hexyldiethanolamine, octadecyldiethanolamine, etc.

Additional amines include ethanoldiethylamine, propanoldiethylamine, ethanoldipropylamine, propanoldipropylamine, ethanoldicyclohexylamine, cyclohexanoldiethylamine, dibenzylethanolam-ine, etc. Ether type aminoalcohols may octylethanolamine, octadecylethanolamine, pentanolamine, hexanolamine, octylethanolamine, cyclohexanolethanolamine, etc.

AMINOALCOHOL ESTER Example 1 1 pound mole of ricinoleic acid is reacted with 1 pound mole of triethanolamine at approximately 180 to 240 C. for approximately to 25 hours, until there is substantially complete esterification. 7

The composition of the formula of such product is indicated by the following formula, in which OH.RCO is the ricinoleyl radical.

AMINOALCOHOL EsTER Example 2 Ricinoleic acid in the preceding example is replaced by methyl naphthenate.

AMINOALCOHOL ESTER Example 3 Methyl abietate is substituted for ricinoleic acid in Example 1, preceding.

AMINOALCOHOL ESTER Example 4 Ethyl oleate is substituted for ricinoleic acid in Example 1, preceding.

AMINOALCOHOL EsTER Example 5 1 pound mole of triethanolamine is reacted with 1 pound mole of ethylene oxide and the etherized amine so obtained is substituted for triethanolamine in Examples 1 to 4, preceding.

AMINOALCOHOL ESTER Example 6 1 pound mole of triethanolamine is reacted with 2 pound moles of ethylene oxide, and the etherized amine so obtained is substituted for triethanolamine in Examples 1 to 4, preceding.

AMINOALCOHOL ESTER Example 7 1 pound mole of triethanolamine is reacted with 3 pound moles of ethylene oxide and the etherized amine so obtained is substituted for triethanolamine in Examples 1 to 4, preceding.

AMINOALCOHOL ESTER Example 7 8 Example 9 1 pound of diethanolamylamine obtained by reacting 1 pound mole of diamylamine with 2 pound moles of ethylene oxide, is employed in place of triethanolamine, in Examples 1 to 4, preceding.

AMINOALCOHOL ESTER Example 10 The sameprocedure is employed as in the preceding example, except that an etherized amine is obtained by treating amylamine with 4, 6 or 8 moles of ethylene oxide, and such etherized amine is employed instead of diethanolamylamine.

AMINOALCOHOL ESTER Example 11 1 pound mole of castor oil is reacted with 3 pound moles of triethanolamine, as described in the aforementioned U. S. Patent No. 2,324,489, under the heading Intermediate hydroxylated amine, Example 1.

aaam

Example 14 One follows the directions of U. S. Patent No.

2,293,494, to De Groote and, Keiser, dated August 18, 1942, to produce anarnine of the following composition:

011 CzH4O CaHa n oznion on Such amine is substitutedior triethanola-mine in the preceding examples.

Am voALqonoL Esme Example 15 1 pound mole of hydroxyethylethylenediamine I is reacted with 3 moles of ethylene oxide, to give the corresponding tetrahydroxylated derivative.

Such compound is employed in place of triethanolamine, in the preceding example.

AMINQALCOHOL ESTER Example 16 The same procedure is followed as in the preceding example, except that a to 7 moles of ethylene oxide are employed instead of 3 moles.

AmmoALconoL Es'rcn Example 17 The same procedure is employed as in the preceding example, except that diethylenetriamine is substituted for ethylenediamine, and treated in such a manner as to eliminate any secondary amino radicals.

and

0116211! H OH H N'JzHlOG .0 021 0] .are substituted for ethylenediamine in the preceding examples.

AMINOALCOHOL ESTER Example 19 In the preceding examples, where more than 1 high molal acyl. radical can be employed, 2 ricinoleyl radicals or the equivalent are introduced into the polyamine alcohol.

WWQQQliQFEfiWE: 7 Example 20 Unsymmetrical Y diphenyl. diethylenetriamine, is

treated ethylene,

oxide and. substitut d for oxyethylat'e d ethylenediainine" in the. hreceging examples.

AMINOALCOHOL ESTER. xam l Symmetrical diacetyl triethylenetetrarnine is treated with 4 moles of, ethylcneoxide andsub: stitutedfor oxyethylated ethylenediamine in the preceding examples.

M EQ PQQHQF ESTE Example 23 Additional examples are preparedin the mannejr previously described, except that one'e'gnploys amingalcohols obtainedby theoxyalkyla tion off morpholine; 1,3 diamino-2-propanol-{2Q nimal-mane: am e hy l r i ai 2-amino-2-methyl L3 propanediol; 2 arnino-2- ethyl-1,3 propanediol; tris (hydroxymethyl)"aminomethanefor piperidine. One may useenough of the olefine oxide for instance, ethylene oxide, to convert all amino hydrogen atoms into hyf droxyethylradicals, or one ma'y'employ a. greater amount so as to introduce ether linkages in'addi tion, or may use glycide instead of ethylene oxide, at least to introduces; terminal radical or radicals ha n a llilfa i at h l f M APQQHQL- 3 5 Example 23 The. same procedureis followed as inExa nple 32, preceding, except that one employs the amines described in Examples 9, 10, 11 and 13 of s. Patent No. 2,306,329, to De Qroote and Keiser, dated December 22, 194,2.

eameecbme we Eatample E4 Soyabean oil, blown soyabean oil, blown castor oil, or blown teaseed'oil is substituted for castor oil in the preceding examples.

in the above examples it is obvious that free hydroxyl radicals maybe present as part of a hydroxyalkyl radical, or as part of the acyl radical of a fatty acid, such as 'ricinoleic acid.

As an example of a preferredtype of raw ma terial, which is effective for use in preparing our new composition and'demulsifier, the following is submitted: We prepare a' mixture of diamine and triamine materials which correspond essentially to either one of the two following type form's.

oncgrn NCZHAO oiH N OHOQH4 w aw Aiter determining the average molecular weight of mil t l We'combine'the same with castor oil in theproportion of '1 pound mole ore-aster oil for 3 pound moles of the mixed amines, pound mole in the latter case being calculated on the averagejmolecul-a'r weight as determined. Such mixture is heated to approximately -269 C -tion. For instance, a basic aminoalcohol ester might'be combined with diglycollic acid so as to produce a salt. Such type of material is not herein contemplated, except to the extent that it is incidental to the formation of an ester. Aminoalcohol esters, of the kind herein contemplated las reactants for esterification with diglycollic acid, have been combined in similar forms with other dibasic acids, particularly phthalic acid in the form of the acid, anhydride, ester, etc. Similarly, in the present instance, one uses diglycollic acid in the same way that phthalic acid, maleic acid and tartaric acid would be employed. For complete description of such procedure, reference is made to U. S. Patent No. 2,154,422, dated April 18, 1939, to De Groote, Keiser and Blair.

In the preparation of esterification products, the esterification reaction may be caused to take place readily upon the application of heat, the reaction .being more rapid the higher the temperature that is employed, but care should be 3 taken not to employ excessively high temperatures which would cause decomposition. The reaction may, if desired, be in the presence of an inert solvent, such as xylene, which may be re- 'moved upon the completion of the reaction.

When water is formed as a reaction product, the esterification reaction may be conducted under a reflux condenser, using a water trap to remove Water as it is formed. The reaction can also be hastened by passing through the reacting materials a dried inert gas, such as nitrogen or CO2. Generally speaking, however, the reactions take place rapidly, quickly, and completely, by simply heating substances to enter into the reaction in desired stoichiometric proportions at a temperature above the boiling point of water, usually between about 180 and 250 0., provided there is no decomposition. The most desirable products are obtained by combinations, in which the ratio of moles of diglycollic acid to moles of particular material reacting therewith, is within the ratios of 1 to 3 and 3 to 1.

Esterification reactions of the kind contemplated are used for the production of a wide variety of esters, resinous materials, sub-resinous materials, and include plasticizers. Attention is directed to the following patents, which are a cross-section of conventional esterification procedure, which can be applied in any instance to the production of the herein contemplated esters.

British Patent No. 422,845, Jan. 14, 1935 British patent to Eckey, No. 500,765, Feb. 15, 1939 U. S. patent to Malm, No. 2,170,030, Aug. 22, 1939 Bradley, No. 2,166,542, July 18, 1939 Barrett, No. 2,142,989, Jan. 10, 1939 Frazier, No. 2,075,107, Mar. 30, 1937 V Sly, No. 2,073,031, Mar. 9, 1937 Bradley, No. 1,951,593, May 20, 1934 Lawson, No. 1,909,196, May 16, 1933 Kessler, No. 1,714,173, May 21, 1929 10 Van Schaack, No. 1,706,639, Mar. 26, 1929 Jones, No. 2,264,759, Dec. 2, 1941 Wietzel, No. 1,732,392, Qct. 22, 1929 Groves et al., No. 1,993,738, Mar. 12, 1935 Attention is directed to a comprehensive article entitled Polyhydric alcohol esters of fatty acids, their preparation, properties and uses, by H. A. Goldsmith in Chemical Reviews, volume 33, December 1943, Number 3.

COMPOSITION or MATTER Example 1 1 pound mole of an aminoalcohol ester, as described under the heading Aminoalcohol ester, Example 1 is reacted with 1 pound mole of diglycollic acid. This is a conventional esterification reaction'and the materials are mixed and heated to approximately to 250 C., with constant stirring, until samples taken from the batch and analyzed, show substantially complete disappearance of a hydroxyl value equivalent to combination with one carboxyl radical of the diglycollic acid. The time involved may vary from 2 to 14 hours. A suitable solvent may be present and any water formed may be distilled ofi continuously during the esterification reaction.

COMPOSITION OF MATTER Example 2 The same procedure is folowed as in the preceding example, except that 2 pound moles of diglycollic acid are used for each pound mole of the aminoalcohol ester. The time 'of reaction may have to be increased moderately.

COMPOSITION or MATTER Example 3 The same procedure is followed as in Example 1, except that 2% pound moles of diglycollic acid are employed instead of 1 pound mole, as in the previous example. The time of reaction may have to be increased moderately and the temperature of reaction increased slightly.

COMPOSITION 0E MATTER Example 4 Comosnron or MATTER Example 5 The same procedure is employed as in Example 4, except that the 3 moles of aminoalcohol ester are obtained by reaction involving 1 pound mole of castor oil and 6 pound moles of triethanolamine. The resultant, considered as representing 3 pound moles, is reacted with 3 pound moles, 6 pound moles and 6%"pound moles of diglycollic acid.

COMPOSITION or MATTER Example 6 The same reactant employed in Example 5, preceding, is reacted with 7 /2 pound. moles of diglycollic acid.

i i l f9 l l I l is reacted with lfpoundl'mole of ,ricinoleic acid '01- f ethyl ricinol'eate and the ifanjiin'oalcolriol' ester a; @biti i i q "Q 3 inoles ofi diglyc ollic acid 'for each 'p'o'und" mole of Example 7 Jlihe same'pro edure\.,is .i 1 lwedas in theEX- .a p es i an ..6. l immediate yprecedi j Q P that the aminoalcoholwester isco tained by a action involving 1, pound molehof castor oil and 9 pound moles of triethanolamine.

COMPOSITION OF MATTER Example 8 An aminoalcoholcesteriprepared. fromricino i acid onethylricinoleatetin themanner describe under the. headineWAmimalcohol ester. .E xample 1a.: is, substituted .forlthe; producteexemplificd, by

Aminoalcohol ester, .Examplelii in fC m D (see Aminoalcohol 'esterflilxample 18, preceding) is reacted with. 1.. pound l mole. ..of. ,ricinoleic l acid l. .or iethylricinoleate iand the. .l aminoalcohol ester soi ohtainedireactedtwith.1, 2,2 9113 llQ lmolesrofidiglycolliciacid for each pound mole of the aminoalcohol ester.

CoMeosrrIoN or MATTER ExampleiO 4. ...1.vp,0lln'd mole of an amine, of the following composition chem v tea I (a-late matte totem on'cze. "ea a canon (see Aminoalcohol e s terfEia'inple'lii, preceding) is reacted with lpoimd lniole of rlcinoleic acid and the aminoalcohol ester with 11 12,? "for 3 1' pound lpou'nd Inole or an amine of the followingtheaininoalcohol ester. 7

It may be well to point out that the amine compounds herein contniplatedfor reaction with diglycollic acid, maybenggnoamino or polyamino mitten tee, is "th parboxy ,.det'ergent formingacid haying at least a yl rad ca .o mono.-

S'and not morevlthan 32M aItbOn, atoms, and the amino nitmgen ,a 0m, m i1is t. J0? b 1519; ,i. e., 1 free from direct linkage withannnsaturated'orjnegativel radical, such as an, acyl. radical, I01 a ar l radical. The R .is an'alkylenle radical hayin at least 2 and not more than. 10 "carbon 'aQO Z and preferably, 2 3 or 4 jcarbqn atQmSL. Th alkylene radical .may be, ponsidered as being derived from an ,ole'finej-oxide," such as ,thosefpreyiously mentioned. Additional reactive olefine X- ides are described in US. PatentlNol 2,208,581, to Hoefielman and dated July '23, 1940; and include among others, gglyc'ide, hexylene ioxide, decene 0Xide e'tc. The. characterfiii'ndicates a; number varying" jirom l to 10, but preferably, from 1 to l. Re'currences of Rxneed notbethe same. For instance, 1 mole'of, triiethanolarnine might be reacted with.3'moles of ethylene oxide, and the, resultant product so obt'ainedmay;be reacted With 3 moles of butylene oxide. ,The aminoalcohol so obtained co'uld be'esterified in the manner previously described. Itis'obviOus, of course, that when 12:15 2 ormore, theqproduct is in essence an este'rifiedfaminoetheralcohol, the expression etheral'cohol being frequentlya'pplied to alcohol-s when a carbon atomchain'isiinterrupted at least once byan oxygenatomh Ether Iin'kages may appearinother; positions, where there is' no direct union with RCO. v v

The simplest reactant herein contemplated is the octenoic acid ester of ethanbldin'aethyltrmine. On the other hand, one may have" a'mino'compounds having 4, 51ori6 'amirioinitrogen "atoms and containing in addition"asl fn'anyi'as. 4"acyl radicalsderive'd' from high molal acids having as many as 32 carbonatoms.

Jar weight range of the monomeric form'may vary Thus, the molecufrom 243 to 10 0r 2,0'ti1nes.suchyalueforjust short of 5,000, or thereabouts. 'Theease'with whichlheatpolymerization of polyhydric alcohols and polyhydric"aminoalcohols takes p1ace,""sug- '"g'ests that condensation polymers obtained by etherizationl may have 'a substantially "higher molecular weight.

. Reference has'beenmace tothe'u'se' of'g'lycifde,

.epichlorhydrin, etc," as" an oxyalk'ylating "agent.

Reference has also been made toreactions which involve etherization in 'wliich glycerol" appearsas a reactant. Thus, R',"previo'us1yreferred to as being an alkylene radical; such as ethylene-"propylene,'e'tc., o'bviously includes radicals obtained from glycerol, or g1ycide,'e't'c., the' hydroxy propylene radical. Hence, in thehereto appended claims, reference to the' propylenei'adical', either "generally "or specifically, is intended to i'n'c'lixde "the hydroxyp'ropylene radical as 'well.

Attention directed toithe fa'ct thatf'in 'the h'el'etb' appended claims, the DTQWSO that'an' ether "linkage be present does 'r'1'ot"1i'1ea'n that "the ether "iinka emust necess rily occur "in theradicar by "Wl'l'ibh the acyl 'r'a'di'al RCO is jo'i ll d "the nearest. bas c;.eiiree a iem-n ieeiaeea ne that the introduction of an acyl radical may be such that the acylcx radicallisijoinedlto for 13 basic amino nitrogen atom, but involves a radical uniting two nitrogen atoms.

At this point'it may be well to re-emphasize the nature of the compounds herein contemplated, the most expedient method of manufacture and the preferred form which represents, in fact, an invention within an invention. The first step involves the production of an acylated aminoalcohol, in which there is present a high molal acyloxy radical, as defined, and also an alcoholic hydroxyl radical. There must be present at least one basic amino radical, and there may be present more than one basic amino radical. Such reactant obtained from the specified raw materials, is esterified with diglycollic acid, so as to yielda fractional ester having present one or more free carboxyl radicals as part of a diglycollic acid group. We have found that the best results are obtained from triethanolamine, heat polymerized triethanolamines, and polymerization products of triethanolamines and glycerol. These are typified 'by the following three formulae, previously pre- The acyloxy group is preferably obtained from an unsaturated higher fatty acid having 18 carbon atoms, and particularly castor oil. Such compounds described from the above reactants along with the etherization derivatives of the 2 polyamines, in combination with castor oil or with glycerol, and employing ricinoleic acid as the higher fatty acid group, give intermediates of outstanding merit. The use of castor oil, being less expensive, is preferred.

We are aware that valuable products suitable for use in demulsification may be prepared by considering the acidic fractional esters herein contemplated as intermediates. Such intermediates can be subjected to oxyethylation with ethylene oxide, propylene oxide, butylene oxide, 'glycide and methylglycide, so as to give watersoluble products. Similarly, such intermediates may be reacted with hydroxylated tertiary amines, particularly triethanolamines, to give acylated derivatives having particularly valuable properties for the purposes enumerated in the present paragraph.

Returning to a consideration of the reactants employed in obtaining the present composition, it is to be noted that in some instances condensation polymerization can take place, insofar that both reactants are polyfunctional. This is not necessarily the case in each instance, as, for example, the aminoester obtained by reaction of ricinoleic acid and diethylethanolamine or oleic acid and ethyldiethanolamine.

On the other hand, where one of the reactants is an esterified aminoalcohol derived from aminoalcohols of the kind described by formulae in Aminoalcohol esters, Examples 1, 14 and 17, it

is obvious that reaction with a dicarboxy acid, such as diglycollic acid, can produce resinous or sub-resinous products. In many instances, such subresinous or balsam-like products are really the most desirable of all, but they'probably do not represent any large'degree of polymerization. In other words, the structural .units appear three or four times over, and in substantially every instance, the molecular weight is distinctly less than 5,000, with perhaps 3,000 as an average figure. In other words, such polymers consist largely of dimers, trimers, tetramers, pentamers, hexamers, and so forth, having molecular weights, by the ordinary melting point depression methods, of less than 5,000. It is also obvious that polymerization may be due to this formation of new ether linkages as well as esterification. In order to produce such sub-resinous low multiple polymers, one need only continue the time of reaction or use asomewhat increased temperature of reaction, provided the esterified aminoalcohol offers opportunity for condensation polymerization by either esterification or etherization.

In light of what has been said, it becomes obviously difficult, if not impossible, to present a formula depicting such more elaborate and more complicated aspect of the invention, 1. e., a formula which would describe the low multiple polymerfas well as the monomer. However,.insofar that such polymer isessentially a, repetition of the structural unit with only a comparatively small change, such as one expects in condensation polymerization, it is intended that the claims herein appended contemplate, in the broadest aspect, both the monomers and the .polymers. It is "our preference to employ esters, wherein there 'is anexcess of unreacted diglycollic acid radicals, compared with basic amino nitrogen atoms. Byipropefselection of ratio of reactants, one may, of course, h'ave'a type of ester which is alkalinein nature, that is, has more basic amino nitrogen atoms present than in esterified diglycollicrcarboxyl radicals. Similarly, one may have a neutral 'salt form, where the number of basic amino nitrogen atoms is just equal to the number of freediglycollic acid radicals, and finally,

one may havethe acidic form, where the number' of free diglycollic acid radicals is greater than the number of basic amino nitrogen radicals. In this connection, attention is directed to the structural formula of the aminoalcohols depicted in Aminoalcohol ester, Examples 14 to 18. In each instance one could introduce at least one acyl group, particularly a hydroxyl acyl group, such as the ricinoleyl radical, and still introduce sufficient diglycollic acid radicals, so that the free radicals resulting from the combination of only one of the two diglycollic acid radicals would be in excess of the number of aminonitrogen atoms present. Our preferred form of reagent is the one which shows either basic properties, or acidic properties, or preferably the latter. Another type which is particularly valuable, is the type in which both represent monomers of low multiple polymers, de-

=sol, anthracene oil, etc.

rived from castor oil, and -the cheapest hydroxyl- 'ated tertiary amine, to wit, triethanolamine'. monomeric form, the resultant of such reactions involving, for instance, "1 mole of 'ricinoleic'a'cid,

2, 3, r 4 molesof-triethan'olamine,and-even'a mole of glycerol, is still distinctly under lgdfil), and even if'the monomeric unit adds several digly'colllc acid radicals, yet after allowing for theeliminationof water in thecondensation polymerization,it becomesobvious that-low multiple conden- 2 T sation polymers will not exceed Weight of 5,000.

Conventional demulsifying agents employed in the treatment'of oil-field-emulsions,=are used'as a molecular such, ;or after dilution with'anysuitable solvent, 1

such as water; petroleum hydrocarbons-such as gasoline, kerosene,'stove oi-l; -a-coal tarproduct, suchas benzene, toluene, xylenatar-acid oil, cre- Alcohols, particularly aliphatic alcohols, such as "methyl alcohoL ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohoL-octyl alcohol,-etc.,'may-be employed as 'diluents. Miscellaneous solvents, such-aspine oil,'carbon tetrachloride,-sulfur dioxide' extract obtained'in' the refining ,ofpetroleum,

etc., may be employed as diluents. similarlyjthe material or materials employeda-s the demulsifying-agent of our process may :be admixed with one or-more ofthe solvents customarily'usedin connection with conventionaldemulsifyingagents.

Moreover, said material or materials-maybe used alone, orin admixture with other'suitablewell known classes of demulsifyingagents.

Itis well known that conventional demulsifying agents may be-used in a water-soluble form, orin an oil-soluble form, or in a ror rr exhibiting both oil and water solubility, 'Sometimes they plated in our process, i's'based upon-its'ability to treat certain emulsions moread-vantageously and at asomewh'at-lower cost than'ispossible'with other available demulsifiers, -or conventional mixtures thereof, 'It'is believedthattheparticular demulsifying agent or treating-agent'herein described will find comparatively limited application, sofar as-the majority of oil-field emul- 'sions are concerned; but wehavefoundthat-suizh a-demulsifying agent has commercial value-as it will economically break or resolve =oil field emulsions-in a number of cases whichcannot be treated aseasily or at so lowa cost'with the demulsifying agents heretoforeavailable.

In practising -our process for resolving petroleumemulsions of the-water-in-oil; type, a 'treating' agent or demulsifying agent of .the kind above described is brought into contact yvitlr or caused -to act upon the emulsion to be treated, in'any of: the various ways, or by any of theyarious ap- Wparatus now generally 'used to resolve i or break petroleum emulsions with alchemical reageritathe above procedure being used either alonepor in combination with :other demulsitying :proeedure,

ssuch as the ieleetrical dehydration process. 7

lhe demuls-ifier herein ccontemplated may be employed in connectionwith what-is commonly lmowln .as down-the-hole tprocedure, :i. e., "bringling zthecdemulsifier in contact with .the :fluids of the well :at the bottom of the .well, or at some :pointzpriortothe emergence of said fluids. This particulartype of application is decidedly feasi- -ble, when lthedemulsifier is used in connection with acidification'of calcareous oil-bearing strata, aespecially if suspended in or dissolved in the acid 'iemploye'd'for acidification.

As meWhat analogous use of our demulsifying agent is'theremoval of a'residual mud sheath which remains after drilling a well Icy-the erotary amelthod. :Sometimes the drilling mud contains added calcium carbonate, or the like, 'to render the mud susceptible toreaction-with hydrochloric acidorathe like, and thus expediteits removal.

'one'preferred andmore narrow aspect of our invention, insofar as it is concerned with de- 'mulsification of petroleum emulsions .of :the water-,in-oil type, is concerned with'the admixture of the diglycollic acid-acylated aminoalcohol esters, as described, with a viscosity-reducing solvent, such as the various solvents enumerated, particularly aromatic solvents, alcohols, ether alcohols, etc., as previously'specified. The word solvent is used in this sense to refer to the mixture, if more than one solvent is employed, and generally speaking, it is our preference to employ the demulsifier in a form representing 40% to 85% demulsifier selected to give a solution or mixture particularly adaptable for proportional pumps or other measuring devices. The following examples will illustrate this aspect of our invention:

Partial ester, as exemplified by composition =of -matte13EXample 9, u.sing Spouud moles of diglycollic acid for each pound mole of 'aminoalcohol ester 70 Cresylic acid 20 Denatured alcohol l10 DEMULsIFmR Example 3 Per cent .Partial esteryas exemplified'by composition of matter,'Example ll,'using 4 pound moles of diglycollic acid for each poundjmole of the aminoalcohol ester -i 'A 'pmatic'petroleum solvent 20 "Is obutyl alcohol 20 .Acetone 15 (The .above :proportions represent percentage lby :weight.)

IFne results obtained with the herein contemplat'ed compounds .give results which are absolutely unexpected .and :unlooked-ior, :in light of the demulsifying action of other com-pounds of apparently .analogous structure. For instance, Sit:isiconvent-ionaltpractice .to.use fractional esters 1 derivd from it'riricinolein or other e'sters, as here- '--in described as reactants, in 4 combination with e er flicarbciiy acids, 'such as phthalic acid, inaie' c damn-maria, 'citracbnic-acid, a zelaic *acid, tl ie-d lycolIic-acid derivatives have given results which are "simply outstanding, i-n comparison with "such other analogous--'partia1 esters. "In

other words, it appears that for someunexpeted reason, the ether grouping of-"-d'igly'eollic "acidin cornbinaticin' with" the 1 carboxy'lid radicals and the remainder of the molecules, give some exceedingly efiective adsorption property ''or I orientation property which 5 gives results so 7 exceedingly unusual.

' FIELD TEST No. 1

an 'o'il producing property located in the stain Government"Wells field,'at"or11'iear' naval, Texas; theemulsion producedcontainedapproximat'ely' %ofemulsion andwa'ter. "The emulsion broke readilyat 100"F.,"usinga demulsifier corresponding substantiallyto Example 4, preceding. The residual oil contained a total of 1"o emulsion or water. The total timeinvolved; both in-inixing ands'ettling; was one 'hour. 'The ratio or drhril'siiier used, o'n-the basis of barrels of recovered oil, was '1 to=l2',500. All told, such re- 'su'lts' represent an improvement of at least"2 5% 'o'verthenext best available compound of the same-structure, but obtained from some other dibasic acid, such-as phthalic, maleic, adipic; etc.,

instead of 'diglycollic;notwithstanding the fact that this latter series of comparative testswere conducted at F. higher in temperature.

FIELn TEST No. 2

On "an oil-producing property located in the Place'do 'Fi'eld, at or 'ne'ar'Plac'edo, Teiras,'the

emulsion" produced contained approximatel of emulsion and water. 'The emuls'ionbroke readily at 70 F., using a demulsifier corresponding substantially to Example l, preceding. The residual oil contained a total of /11% emulsion 'or water. "The-total time involved,- both in mix- "On an on-producing property located in'the McFaddin Fieldyat or'near McFaddinjTexas} the emulsion produced contained-approximately 20% of ehiulsion ;and water. The emulsion broke readily at 70" F., using a-de'muls'ifier corresponding substantially to Example 4;preceding. The residual oil'contained a total of-1- o-% emulsion orwat'er. The total time inyo1ved, b'othin mixing and settling, was one hour. a The ii'atio of demiilsifier usm, on the basis of barrels of recoverd oilfwas 1 to- 3,000. 'All told, such results represent-am improvementof at least 25% over thniibbst available compound 'of'the same structure, *buir obtained from some other -dibasic acid, such as "phthalicfmaleicg adipic, etc., instead of diglycollic, notwithstanding the fact that this latter" se'ries'of' comparative testswere conducted at 30F."-higher in ten'iprature.

'Th'e "a1hifiba1c6h()1 esters herein contemplated for reactionwith {d-iglycollic acid, -inayrepresent a 11i'ciu3l'1y'd1'" ic alcohol" or a polyhyd'ric alcohol.

w er as, r1 1 a polyl ii amine. *Other' examples have 'ben-describdin which more than 3 alcoholic hydroxyls could be resent; for instance, esters 'of airiines cbtained 'byfie rig -t'r ithano1amine f th 'g1ycide'af1d then subjectingsiih intermediate to es'terification. r

If an alcohol is indicated by the formula:

Y" (OH) n where n indicatesthe number 2 or more, and if diglycollic acid be indicated for convenience by the formula X"(COOH)2 then the r'eaction between a polyhydric alcohol and A diglycollic acid will result i na compound Which may be indicated by the followingfdrmula:

where n indicates the number 1= or more, 5 and which is, in reality;a contraction of a more elaborate structural formula; in Whioh'X and"Y a-re "joined 'bya carboxyl radical orresidue. Assumiiig, however, as would be true in the majority of cases; that "the' alcohol actually "would 1 be a polyhydric alcohol, then examination"'reveals that the formula might result in f a'combination,

in which there were *neither residual carboxyl radicals, nor residual hydroxyl'radicals; or might result in compounds 'inwhich there were residual hydroxyl radicals, or compdundswhere there might be residual carboxyl radicals, and noresidual hydroxylradicala or there might beboth.

This is indicated-by the following:

- (Y.X) 'q'(OH) 11. (TX) ri'coo n) m (0H) M YX) 4(COOH) m" in which 'q' indicates a small whole number (one in' thecaseofa'monomer} 'and probably not over 10, and usually 'less tha nfi) {and -'m' and n" indicate the ht imber' I GI mOTQ-"afid 'm" a'fid n" indicate a small or mddrately sized' Whole niimbe'r, such as 0, 1 or more, but in i any event; probably a numberriot inexce'ss of 10. Actually,; thes 'preferable' type of reagent 'would'be more apt to contain less than 20,"afid' in factj less than 10 free hydrOXyTiaGiCals. "It is not necessar toremark thatresiduaicarboxyr'radicals can be per- 'm'itted-to remain as sucr cr can be convertedin any 'suitable' 'mar'inen'into "an ester. Conversion into the ester'wouldbe cy-means of a monoh'ydric alcohol, such as 'rnetliyl "alcohol, ethyl alcohol, propyr'alccnol, butyl aleonoi, he'xyr'alcohoretc.

Forpractical" purposes, however; we have 'f'oimd that theniost dsirable prodiicts' are obtained by coiiibinatioha in which the ratio of the 'alcoholic reactant to the acid 'is'Wi'th'in' "the ratio"'of 3 to 1 and 1 to 5, and in which the molecular This is simply another way of stating that it is preferable that the product be of the sub-resinous type, which is commonly referred to as an A resin, or a B resin; as distinguished from a C resin, which is a highly infusible, insoluble resin (see Ellis, Chemistry of Synthetic Resins (1935), page 862, et seq.)

In recapituiating what has been said previously, the sub-resinous, semi-resinous, or resinous product herein contemplated may be indicated by the following formula:

in which the characters have their previous significance, and y represents a small whole numher not greater than 3, and at represents a small whole number not greater than 5; q is a small whole number less than 10, and preferably 1 to 5; or an organic radical derived from a monohydric alcohol.

Sub-resinous materials having the repetitious unit appearing three to ten times and having a plurality of free carboxyl radicals or free hydroxyl radicals, or both, are Well known in a variety of forms and find practical application in demulsification of crude oil emulsions. Generally speaking, the molecular Weight of such sub-resinous materials, regardless of class, is less than 10,000 and is more apt to be in a range of 3,000 to 5,000 as an upper limit,

A more elaborate description of this typ of material appears in numerous patents concerned with demulsification of crude oil emulsions, and reference is made to such patents for a more elaborate description.

Attention is directed to our co-pending applications Serial Nos. 604,993, 604,994, 604,995, 604,996, 604,997, 604,998, 604,999, 605,000, and 605,001 filed July 13, 1945, all of which are related to the present application, in that such co-pending applications are concerned, among other things, with the breaking of oil field emulsions by means of demulsifiers containing a diglycollic acid radical. .It may be well to emphasize that, by following the procedures outlined, one may obtain compounds which .are actually water-soluble. In a broader sense, then, the compounds herein contemplated may be oil-soluble, or oil-insoluble; they may be water-soluble, or water-insoluble, and may,'in fact, show little or no solubility in either oil or water. This latter statement is something of a paradox, but it is to be emphasized that these esters are frequently effective at enormous dilutions when used as demulsifiers for water-.in-oil emulsions. For isntance, we have repeatedly conducted experimental tests, in Whichthe ratios employed vary from 1 part of demulsifier to 10,000, and at times, up to 50,000 parts of emulsion. For practical purposes, when a compound is soluble in less than 1 part to 10,000, it is commonly referred to as insoluble, but in such extremely dilute range, the word insoluble is purely relative, and perhaps meaningless.

Attention is directed to the fact that blown oils derived from higher fatty acids or higher fatty acid glycerides, and particularly blown castor oil, may be employed as a source of a detergent-forming monocarboxy acid acyl radical or acyloxy radical, in the preparation of the herein contemplated compounds. In innumerable instances, the

replacement "of castor oil or an analogous ester or ricinoleic acid by the drastically-oxidized or blown product, gives a compound which is particularly valuable as a demulsifying agent for petroleum emulsions. This applies with equal force and effect to blown dehydrate'd castor oil and is analogs in the form of 'the correspondin acids or esters.

The new chemical products or compounds herein described forming the subject-matter or our divisional application Serial No. 707,987, filed November 5, 1946.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of the resultant obtained by esterification between diglycollic acid and a basic acylated aminoalcohol, in which there is at least one occurrence of the radical in which RC0 is the acyl radical of a monocarboxy detergent-forming acid having at least 8 and not more than 32 carbon atoms; the amino nitrogen atom is basic; R. is an alkylene radical having at least 2 and not more than 10 carbon atoms; and n is a small whole number varying from 1 to 10; and the molecular weight of said aminoalcohol in monomeric form being at, least 243 and not over 4,000, and the molecular weight of the diglycollic acid ester being not in excess of 5,000.

2. A process for breaking petroleum emulsions of the Water-in-oil type, characterized by subjectin the emulsion to the action of the polymeric resultant obtained by esterification between diglycollic acid and a basic acylated aminoalcohol, in which there is at least one occurrence of the radical in which RC0 is the acyl radical of a monocarboxy detergent-forming acid having at least 8 and not more than 32 carbon atoms; the amino nitrogen atom is basic; R is an alkylene radical having at least 2 and not more than 10 carbon atoms; and n is a small Whole number Varying from 1 to 10; and the molecular weight of said aminoalcohol in monomeric form being at least 243 and not over 1,000, and the molecular weight of the diglycollic acid ester being not in excess of 5,000.

3. The process of claim 2, wherein RC0 is the acyl radical of a higher fatty acid.

4. The process of claim 2, wherein RC0 is the acyl radical of a higher unsaturated fatty acid.

5. The process of claim 2, wherein RC0 is the ricinoleyl radical.

6. The process of claim 2, wherein RC0 is the ricinoleyl radical, and R is an ethylene radical.

'7. A process for breaking petroleum emulsions of the Water-in-oil type, characterized by subjecting the emulsion to the action of a polymeric resultant obtained by esterification between diglycollic acid and a basic acylated aminoalcohol obtained in turn by an esterification reaction between one mole of triricinolein and approximately 3 moles of triethanolamine.

8. A process for breaking petroleum emulsions of the wate'r-in-oil type, characterized by subjecting the emulsion to the action of a polymeric resultant obtained by esterification between diglycollie acid and a basic acylated aminoalcohol ob- 21 22 tained in turn by an esterification and etherifica- REFERENCES CITED tron reactions between 1 mole of trincinolein and approximately six moles of trie m The following references are of record in the 9. A process for breaking petroleum emulsions file Of this P t n of the water-in-oil type, characterized by subject- 5 UNITED STATES PATENTS ing the 811111181011 to the action of a polymeric resultant obtained by esterification between Number Name Date diglycollic acid and a, basic acylated aminoalcohol 2,154,422 e Groote et a1 Apr. 18, 3 obtained in turn by an esterification and etherifi- 2,154,423 De Groote et a1 13, 1939 cation reactions between 1 mole of triricinolein 10 2,176,703 De Groote at 911 1939 and approximately 9 moles of triethanolamine. 2372797 Segessemann 3, 1945 mvm DE GRQQTE ,385,969 De Groote et a1. Oct. 2, 1945 ARTHUR F. WIRTEL. 

